TW402622B - Weatherable resinous composition having improved opacity and impact strength - Google Patents

Abstract

A thermoplastic molding composition comprising a grafted rubber and a copolymeric matrix is disclosed. The composition is characterized in that its grafted rubber includes a substrate, a first grafted phase and a subsequent grafted phase which are sequentially grafted to said substrate. The substrate which contains a crosslinked elastomer is grafted with a first grafted phase and with a subsequent grafted phase, both phases containing copolymers of at least one vinylaromatic monomer and at least one member selected from the group consisting of (meth) acrylonitrile and alkyl (meth)- acrylate. The relative rations of the monomers making up the copolymerized phases differ one from the other. The grafted rubber is present in particulate form having a weight average particle size of about 0.1 to 1.0 microns. The composition features improved impact strength and reduced opacity.

Description

40262;

Supplemented Examples in Chinese-Enel. II (Submitted on January I !, 2000) Example Patent f Request No. 88106795 ROC PaMit Appln. No. 88106795 Arresting also. 4 ^ 都 · 你丨 'Lingtai-Saki Pieces-5. Description of the Invention (13) The representative composition of the present invention has been prepared and its properties have been measured. The measurement results are shown in the table below. All of the compositions represented by the present invention and the comparative examples, and a substance white contained 36.5 weight 1% graft rubber and 63.5% copolymer substrate. The total rubber content in all compositions remained fixed at 25% by weight of the composition. This data can be used for comparison between the composition of the present invention and the first graft phase without acrylonitrile, that is, the first graft phase contains only stupid ethylene (Comparative Example of the corresponding composition of c-υ). A corresponding composition containing 30% of acrylonitrile in the grafted phase (comparative example, the amount of acrylonitrile put in the composition is beyond the scope of the present invention. The notched impact strength of the composition is in accordance with the method of DIN 53,453 Measured at 23 ° C in injection molding standard small blocks. These blocks are injection molded at 25 ° C or 280t. 各 The ingredients used in the examples are as follows: A weight average A rubber with a particle size of 0.4 micron, which contains a styrene / acrylic copolymer grafted on the core-shell structure matrix. The core contains styrene and the shell is a cross-linked polyacrylic acid. The relative amounts of styrene and acrylonitrile in the dendritic phase (8 / such as ratio) The f difference between Examples 1, 2 and 3 (representing the present invention) and Comparative Examples C-1 and c_2 is the same. The number of S / AN is average And weight average molecular weight are each kg / mole and 108 kg / mole. The core-shell junctions used in the examples The amount of styrene as the core in the core is 5% of the core-shell structure weight. Ί -------- Q (please read the precautions on the back before filling this page). -F, ί I n I an 1 I λα.-^ Βϋ I ϋ nn ϋ an nn 1 i = 口惠 ^ 一 、-Ｍ 氏 度 向 向 关 关 格 X 297 mm) Staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives B7 λ »/ · ^ ιλ ml · m-Description of the Invention (]) This hair month is about thermoplastics containing grafted rubber: the other is-a composition whose graft phase is limited in order :: Later: The invention sincerely reveals `` species containing grafted rubber and copolymer beauty; fcf is a y compound. The thermoplastic molding group fmei of the ultrafine substrate of this composition is fmei W Μ — Γ which The graft rubber comprises: an elastomer cross: soil: a graft phase and subsequent grafting onto the substrate. Preferably, the substrate preferably includes a crosslinked core and contains at least one ethylenic group. Polymerization of aromatic monomers = one = phase and subsequent grafted phase both contain at least one ethyl 1 ΐΓ: = (: group) acrylic axis (methyl) propyl acetate, and, + The relative proportions of monomers in the same phase are different. Graft rubber exists in the form of granules. The composition is characterized by improved impact strength and reduced opacity. Background of the invention F can be early: f Processing of styrene / nitrile copolymer (SAN) by incorporating ΓΓ Γ impact f. 纟 ABS polymer, the use of two dilute σ compounds to make the rubber hard, most obviously at low temperatures, the aging properties make These substances are not required in more demanding applications. In some of these applications, the successful use of cross-linked acrylic acid esters is known as the ASA copolymer. Such applications are described in the United States ^ j, 055, 859 M_] 26 (), 135 #Di, 9n, 882 mw Preparation of a better crosslinked rubber as a grafting base (㈣) in Cingben County, suitable for 210x297 mm ]--

V. Description of the invention (2) Ester polymer, and then graft the styrene and the printing liquid of the employees' cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to the prepared latex. The material is preferably milk # 梁 式 、 Larger hardness and lower shrinkage are related to the micro-flatness, which is a kind of coarse polypropylene latex with an average particle size of about 150 to _ millimeter particle size distribution as the graft =. Moreover, it is marked in this hairpin In the chapter is a U.S. patent == A-based composition, which contains two different graft copolymers and hard copolymer SAN components on the "4", and its glass transition temperature and chamber Wen Zhi interprets the term relative position! Hard and "soft, part." Hard, means higher than room temperature, soft, means lower than room two, and the outer shell structure includes a multi-layer shell Structure. Includes a hard-and-emulsified heterophasic structured emulsified copolymer to be disclosed in the articles referenced by Ep534, 2i2, and II. Therefore, it is known in the art to have the hardness of polystyrene: Xinxiao Likou No.- Graft copolymer of a layer of acrylonitrile shell and an outer SAN shell. Thoughtfully, article 212 reveals a Monomorphic system, Lizhong particles measured below 0: 2 microns and have a styrene ethyl core. In one example, Chapter 212 丨 revealed that the styrene core is used as the graft base, and the first two shells are used as the acrylic A four-stage graft copolymerization method of dilute butyl vinegar, the second shell is styrene, and the third shell is styrene / acrylonitrile. &Quot; And the current relevant is the joint trial November 11, 1997 The filed patent applications US series number 08 / 974,541 and 1997 filed 955,857, both of which were disclosed to Bayer and both related to weathering compositions containing a grafted rubber component. DETAILED DESCRIPTION OF THE INVENTION- 4 This paper size is applicable to China National Standards (CNS) A4 (210X297mm) Please read the notes on the back of the% and then order c: 't

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Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Printed by Consumer Cooperatives V. Description of the Invention (3) The present invention relates to a thermoplastic molding composition comprising a graft rubber and a copolymer substrate, wherein the graft rubber includes a crosslinked elastomer matrix, a first The graft phase and subsequent graft phases that are then grafted onto the substrate. The first and subsequent graft phases are chemically different from each other. The preferred matrix comprises a favorable cross-linking core comprising a polymerization product of at least one vinyl aromatic monomer, and a layer comprising a cross-linking selected from the group consisting of polyalkylacrylates, polyhydrodienes, and polydienes A rubbery shell, and wherein the first graft phase comprises at least one ethylenic aromatic monomer and at least one member selected from the group consisting of (meth) fluorene and methacrylic acid (meth) acrylic acid Of the copolymer relative to the weight of the first graft phase, the monomer polymerization product is present at least 75% and the member polymerization product is present at least 25%, and the subsequent graft phase contains At least one vinyl aromatic monomer and at least one copolymer selected from the group consisting of ^ meth) acrylonitrile and alkyl (meth) acrylate members relative to the weight of the latter graft phase, The polymerized product of the vinyl aromatic monomer is present in an amount of about 60 to 75% and the polymerized product of the member of the family is present in an amount of about 25 to 40%, wherein the first graft phase is relative to the subsequent The weight ratio of the graft phase is 1/4 to 4 /], the graft rubber Exists in the form of particles with a weight average particle size of about 1 μm, where the substrate contains at least one vinyl aromatic monomer and at least one selected from the group consisting of (T-based) acrylic and fluorenyl (meth) acrylate A family of monomer-forming polymerization products. In a preferred embodiment, the present invention relates to the above-mentioned thermoplastic molding group. (1)] 5 to 50% by weight (pbw) of the above-mentioned graft rubber and ⑴) 85 to 50 pbw of the above-mentioned substrate, the percentage is relative to the total amount of (1) and ⑴). -5 This paper size applies to China National Standards (CNS) A4 specifications (2mx297 public wide (please read the precautions on the back before this page) Μ, 1T. »Ml m (I m A7 V. Description of the invention (4) (i) Graft rubber and its preparation: The graft rubber composition includes a matrix (S) on which it is grafted: a first graft phase (P)) and a subsequent graft phase (P2). The graft phase is then Graft onto the substrate in the usual way. Basically, the first graft phase is polymerized in the presence of the matrix to produce a precursor, and the subsequent graft phase is polymerized in the next step and grafted onto the precursor. Preparation Both the matrix method and the grafting method are technically used and well known. Related information is available at ABS Resin, Stanford Research Institute, Report No. 20, December 1966, Muller RG, Takaoka, S and Encyclopedia of Polymer Science and Engineering , 2nd edition, volume 1, pages 400-405 (1985). The weight ratio of the matrix to the total graft phase, the (S) / (P1 + P2) ratio is preferably 60/40 to 90/10. Within the range, the best ratio is about 70/80 to 30/20. The weight ratio of the first phase and the subsequent phase to each other (P1 / P2) is in the range of 20/80 to 80/20, and the optimal range is 33/67 to 67/33. The matrix (S) is characterized in that it contains an elastomer crosslinked rubber. In a preferred specific example The matrix contains a core (C) and a shell (SH). In this preferred embodiment, the weight ratio relationship (C) / (SH) between the core and the shell is in the range of 1/99 to 25/75. Economy The printed consumer matrix of the Ministry of Intellectual Property Bureau ’s Consumer Cooperative is basically a crosslinked elastomer that contains at least one member selected from the group consisting of polyalkylene acrylate, polyhydrodiene, and polydifluorene. The core contains a core and a shell. In a preferred embodiment of the invention, the core (C) is polymerized by any known method from at least one member selected from the group consisting of styrene, α-methylstyrene, cyclohydrostyrene and cycloalkylated styrene. The core -6- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm) Family composition _B7 V. Description of invention (5) It is best to crosslink; this crosslink can be achieved by known methods The shell (SH) is basically a crosslinked rubber that surrounds the core. It is selected from the group consisting of polyalkyl acrylate, polyhydrodiene, and polydiene moxibustion. The core-shell structure manufacturing method is known in the technology. Related information is available in patents 3,793,402 and 5,384,361 and polymer materials science and engineering = China 0,583 (199〇), which is hereby incorporated by reference and found in application 1,340,025. National Patent No.-Graft Phase (P1) contains at least one species selected from the third group (3Gp) Copolymer formed by at least one monomer selected from Group 4 (4GP) monomers, in which Group 0_ (3gP) monomers include styrene, a_f-based styrene, cyclohydrogenated bicyclic chemical styrene, Group 4 (4GP) monomers include (fluorenyl) acryl and methacrylate: methyl acrylate. Relative to the weight of the first graft phase (ρι), the amount of the third: (3GP) comonomer is at least 75%, and the fourth group is relative to the weight of the first graft phase (1) The amount of (4GP) comonomers is at least 25%.) The subsequent graft phase (P2) comprises at least one monomer selected from the fifth group (5Gp) and at least one monomer selected from the sixth group (6GP). Copolymers, in which the fifth known (5GP) monomers include phenethylhydrazone, a-methylstyrene, cyclic hydrogenated styrene and% alkylated styrene, and the sixth group (6Gp) monomers include (methyl) Acrylonitrile and methyl methacrylate. The amount of the comonomer of the fifth group (5GP) is about 60 to 75% with respect to the weight of the subsequent graft phase (P2), and the sixth group is relative to the weight of the subsequent graft phase (P2). The amount of (6Gp) comonomer is about to 40%. The first graft phase (P) and the subsequent graft phase (P2) are chemically different from each other. The scale is suitable for Shicai Guanjia County (CNS) Eighty Four Secrets (2 297 mm) (please read the back first) Note on this page] 7 ^ 1 This: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs—1T ---------------

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Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (6) The same. The weight ratio of the first graft phase to the subsequent graft phase is (pl) / (p2) is] / 4 to 4/1, and the optimal ratio is 1/2 to 2/1. The grafted oak leaves are present in the form of particles having a weight-average particle size of about 0.01 to 1.0, preferably 0.25 to 0.65 microns. The σ substrate contains at least one comonomer selected from the group consisting of styrene, methylbenzene, hydrogenated styrene, and cyclo-fired styrene (M), and at least one selected from (meth) acrylic Co-monomer of dilute nitrile and methyl methacrylate family (MX2). The weight ratio of (Mχι) / (Μχ2) ranges from 0 to about 65/35. The composition according to the present invention may contain conventional and effective amounts of general additives, the effectiveness of which is known in thermoplastic elastomer molding compositions. I The graft rubber of the composition of the present invention can be borrowed in the presence of an elastomer matrix to two kinds of styrene, α-methylstyrene, cyclic hydrogenated styrene, and cyclic fired styrene, such as p-fluorenyl styrene and The third butyl styrene is prepared by graft copolymerization with at least one (fluorenyl) propyl «and methyl methacrylate, preferably in the form of a core-shell structure. Because the graft yield cannot be reached in the graft copolymerization, the polymerization product obtained by the graft copolymerization always contains a part of the free, graft copolymer (for the sake of convenience, later grafting in this paper Equivalent to SAN). However, for the purposes of the present invention, the term, grafted rubber, is applied only to rubbers where the copolymer is actually grafted. The proportion of the 'graft copolymer' in the polymerization product obtained by the graft copolymerization can be measured by the general method of extracting a free, non-grafted copolymer by methyl ethyl ketone, for example. This paper size applies to China) A4 size (2 丨 〇x297 ^ y (Please read the precautions on the back before this page) > ^ 第 ------ ΐτ ------------ --- A7 4§2 $ 2 ^ __ V. Description of the invention (7)

Moore, Moyer and Frazer, Appl. Polymer Symposia Issue 7, page 67 and subsequent pages (1 968) have described the principle of this separation method. Herein, the degree of grafting is equivalent to the percentage of the grafted SAN which is chemically bonded to the grafted branch of the grafted SAN copolymer based on the total graft rubber. This technique is well known and the degree of grafting can be calculated. The particle size according to the present invention is a weight average particle size, which is measured by ultracentrifugation, such as the method according to W. Sclioltan and H. Lange, Kolloid-Z und Z. Polymere 250 (1972), 782-796. Ultracentrifugal measurement can obtain the cumulative mass distribution of sample size. From this, the weight percentages of particles that are equal to or lower than a certain size can be measured. The cross-linked branch rubber used as a substrate in the article of the present invention can be prepared in a conventional manner by a method known in the art. Crosslinked rubber is a member selected from the group consisting of polyacrylic-C2-8-alkyl esters, polyhydrodiene, and polydiene. The matrix preferably comprises a glass transition temperature measured by DSC method (K .. H. Illers, Makromol. Chemie 127 (1969), page 1) below 0 ° C, preferably below -20 ° C, more specifically an acrylate polymer below -30 ° C. Suitable alkyl acrylates are those alkyl groups having 2 to 8 carbon atoms, most preferably alkyl groups having 4 to 8 carbon atoms. Specific examples are n-butyl acrylate and 2-ethylhexyl acrylate. Acrylates of individual compounds or a mixture of each other can be used. Cross-linking of the rubber matrix can be achieved by known methods such as those related to cross-linking with the shell below. In a preferred embodiment where the matrix comprises a core-shell structure, the crosslinked core phase is preferably made by conventional emulsification techniques well known in the art. I want to use -9-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before this page)

'1T Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 A B7 丨 Jie --- 5. The monomer of invention description (8) is at least one selected from the group consisting of styrene, α-methylstyrene, and cyclic hydrogenated benzene. Members of the ethylene and cycloalkylated styrene family, such as p-fluorenylstyrene and tertiary butylstyrene. Crosslinking can be achieved by incorporating a small amount, usually 0.5 to 3% relative to the weight of the core, preferably 0.5 to 3% of any multifunctional monomer crosslinker known in the art. Examples include triallyl trimerate, diallyl cis butyrate, and divinylbenzene. The shell is a crosslinked rubber selected from the group consisting of polyacrylic-C2_8-alkyl esters, polyhydrodiene and polydiene. The housing preferably contains an acrylic polymer having a glass transition temperature below 0 ° C, preferably below -20 ° C, and more particularly below -30 ° C. The glass transition temperature of the polymers that make up the shell can be measured by the DSC method. Suitable alkyl acrylates for the preparation of acrylate polymers are those alkyl acrylates having 2 to 8 carbon atoms, most preferably alkyls having 4 to 8 carbon atoms. Specific examples are n-butyl acrylate and 2-ethylhexyl acrylate. Acrylates of individual compounds or mixtures of each other can be used. In the preparation of the core-shell phase, the monomers constituting the shell are polymerized in the presence of a core polymer prepared in advance. In order to obtain a better cross-linking of the acrylic polymer, based on the total amount of monomers used to prepare the graft matrix, the polymerization reaction is preferably from 0.5 to 10% by weight, preferably from 0.5 to 3% by weight. The copolymerization of multiple, functional groups, preferably trifunctional monomers, is performed in the presence of a monomer which is crosslinked and then grafted. Suitable difunctional or polyfunctional cross-linking monomers are those cross-linking monomers which contain two or more, preferably three, ethylene double bonds which are copolymerizable and are not conjugated at the 1,3-position. An example of a suitable cross-linking monomer is 10- This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm). Please read the notes and notes before reading

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

V. Description of the invention (9 alkenylbenzene, cis-butenedioic acid ester and diacid dipropionate: 7: yl :, trans-butyric acid, dipropionate, and three dipropyl groups. Trimethylpropyl and Isocyanurin I ---, ------ 、 Packing-- (Please read the notes on the back first to save ^! ^ This page) According to the present invention, I want to borrow eve ^ _ _ The preparation of graft rubber can be carried out according to the following methods. The parent-elastomer matrix core-shell structure is specifically silk. Within the limit of 1Π 〇 ^ Λ ^ first in the aqueous emulsion from 20 to the Ministry of Economic Affairs intellectual property Printed by the Bureau ’s Consumer Cooperative Cooperative Department from 50 to 200, using conventional methods to polymerize vinyl aromatics “forms a core (preferably cross-linked) to obtain vinyl aromatic core I σ. The use of ceremonial agents such as alkanoic acid or arylaryl canic acid is known as salt pain, sulfuric acid vinegar, lutein acid fatty alcohol vinegar, salts of fatty acids of higher carbon number with one carbon atom. Or rosin soap. It is preferably a sodium salt of an alkylene acid or a sodium salt of a fatty acid having 10 to 18 carbon atoms. Advantageously, it is emulsified based on the monomer used to make: the core polymer The amount of the agent used is from 0 to 5 weight%. 'Especially from 0 to 2% by weight. In general, the ratio of water: monomer is # 50. 1 to 0.7:!. In particular, the polymerization used The perturbation of the reaction is as persulfate, such as potassium persulfate, but a redox system can also be used. Generally speaking, based on the monomer used to prepare the core, the amount of initiator used is from (U To i% by weight. Other available polymerization reactions 4 plus 剤 are conventional buffer solutions, such as sodium argon carbonate and sodium pyrofill, to increase the pH to about 6 to 9 'and molecular weight regulators from 0 to 3% by weight. For example, mercaptan, weight oil or dimerized α-methylstyrene. Within the above range, choose precise polymerization conditions such as properties, addition speed, and emulsifiers, initiators and other dosages as appropriate Jiao 11-This paper is a financial standard of 11 financial standards (CNS) Α4 · _ (21QX297 Gongchu) 40262 ^ ---------- V. Description of the invention (〗 〖 The obtained latex reaches the desired particle size. 俜 In the parent axis, the shell can be 11 polymer rubber, preferably == polyethylene In the presence of a aryl aromatic core, one or more polymers can be polymerized using the succinct ceremonial umbrella method. The polymerization temperature is equal to the base (meth) acrylate. The temperature used to make the core is Use: Use initiator, buffer solution, cross-linking agent, and surfactant. The weight ratio of the outer quilt to the core is preferably from 75/25 to paraffin. In the presence of cross-linked rubber, the polymer is polymerized. Contains at least one monomer selected from the group consisting of vinylidene vinyl, cyclic pure styrene ethyl p-T-phenylacetophenone = butylacetophenone (3GP), and at least one species selected from the group consisting of (f-based) acrylic and Monomer system of monomers of formamidine methacrylate (4Gp) to prepare graft rubbers. The weight ratio of the first group monomer to the second group monomer is stated above. It is preferred that the graft copolymerization reaction in which the graft phase is connected to the cross-linked substrate is performed under the usual condition τ in an aqueous emulsion. The graft copolymerization reaction can be carried out, for example, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the presence of a core_shell structure with a specified particle size, the polymer can be polymerized by at least one selected from the group consisting of styrene, Diluted, cyclic hydrogenated styrene and triethylated acetophenone Group 3 (3Gp) monomers and at least one species selected from Group 4 (4GP) including (meth) propanoic acid and methyl propionate Monomer preparation-graft phase. This polymerization reaction can be carried out at 20jLi00t, preferably 50 to 80C, using an emulsion polymerization reaction known as A and used. Conventional initiators (for example, water-soluble peroxides, such as potassium persulfate and azo compounds, such as azo-12- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 M262L · _ £ Z_ V. Description of the invention (11) Redox based on bisisobutyl nitrile) or using oil or water-soluble oxidizing agent (such as p-isopropyl benzene hydroperoxide) and reducing agent (such as glucose or sodium bisulfite) Systems, and optional activators (such as iron sulfate); surfactants (such as alkyl sulfate, alkyl sulfonate, and fatty acid soaps such as sodium lauryl sulfate or sodium oleate); buffer solutions (such as carbonic acid Sodium hydrogen) and polymer molecular weight modifiers (for example, n-dodecyl mercaptan), all of which are well known in the art and can be used in conventional amounts during emulsion polymerization to achieve the desired characteristics. The monomers of the third group (3GP) and the fourth group (4GP) can be introduced in a single quick filling method, preferably in fractions over a period of time, and most preferably introduced as a metered fluid. The weight ratio between these monomers (3GP) / (4GP) is in the range of 95/55 to 75/25, preferably 90/10 to 80/20. The weight ratio of the first graft phase (P1) to the rubber matrix (S) is (P1) / (S) is in the range of 0.15 / 1 to 0.5 / 1, preferably 0.30 / 1 to 0.45 / 1. In the presence of a previously prepared graft matrix (S on which P1 has been grafted), it is preferred that the matrix (S) comprises a core (C) and shell (SH) structure and has a first graft phase ( P1) is grafted thereon by polymerizing at least one monomer selected from the group consisting of styrene, α-fluorenylstyrene, cyclohydrostyrene, and cycloalkylated styrene (5GP) and at least one selected from the group consisting of (fluorenyl ) Acrylonitrile and methyl methacrylate (6GP) monomers were used to prepare the subsequent graft phase (P2). This polymerization reaction can be carried out in a known and customary emulsification polymerization reaction under the reaction conditions and the presence of the above-mentioned polymerization assistant for the first graft phase (P1). The monomers of the fifth group (5GP) and the sixth group (6GP) can be introduced in a single rapid filling method, preferably divided into several parts over a period of time, and the best is to guide them as a metering fluid. -This paper size applies to Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before this page)

Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (] 2), enter. The weight ratio between these monomers (5GP) / (6GP) is in the range of 75/25 to 60/40, preferably 75/25 to 70/30. The weight ratio of the subsequent graft phase (P2) to the rubber matrix (S), that is, (P2) / (S) is in the range of 0.15 / 1 to 0.5 / 1, preferably 0.30 / 1 to 0.45 / 1 . Chemically, the first graft phase (P1) and the subsequent graft phase (P2) are different from each other. As discussed above, the 'composition according to the invention comprises a styrene-based copolymer substrate comprising at least one member selected from the group consisting of styrene, α-methylstyrene, cyclohydrostyrene, and cycloalkylated styrene. A copolymer of a monomer of one group and at least one monomer selected from a group 2 monomer comprising (meth) acrylonitrile and methyl methacrylate. The weight ratio of the monomers of the first group to the monomers of the second group has been stated above. During the graft copolymerization reaction to prepare the grafted rubber component, the formed free, non-grafted copolymer may also form part of the substrate. The weight average molecular weight of the hard copolymer substrate is preferably about 50 to 250, more preferably 80 to 150 kg / mole. The mixing of the ingredients for preparing the composition of the present invention can be carried out by a conventional method and using an apparatus well known in the art. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For other ingredients, the composition may contain any customary additives such as fillers, other compatible plastics, antistatic agents, antioxidants, refractory agents and lubricants. The conventionally effective amount of the additive that can be used is preferably from 0.1 to about 30% of the total relative to the total weight of the graft rubber and the substrate. The invention is illustrated by examples. In these examples, parts and percentages are based on weight unless otherwise stated. -14-This paper size applies Chinese National Standard (CNS) M specifications (210X297 mm> 40262)

Supplemented Examples in Chinese-Enel. II (Submitted on January I !, 2000) Example Patent f Request No. 88106795 ROC PaMit Appln. No. 88106795 Arresting also. 4 ^ 都 · 你丨 'Lingtai-Saki Pieces-5. Description of the Invention (13) The representative composition of the present invention has been prepared and its properties have been measured. The measurement results are shown in the table below. All of the compositions represented by the present invention and the comparative examples, and a substance white contained 36.5 weight 1% graft rubber and 63.5% copolymer substrate. The total rubber content in all compositions remained fixed at 25% by weight of the composition. This data can be used for comparison between the composition of the present invention and the first graft phase without acrylonitrile, that is, the first graft phase contains only stupid ethylene (Comparative Example of the corresponding composition of c-υ. This data can also be compared with the first composition A corresponding composition containing 30% of acrylonitrile in the grafted phase (comparative example, the amount of acrylonitrile put in the composition is beyond the scope of the present invention. The notched impact strength of the composition is in accordance with the method of DIN 53,453 Measured at 23 ° C in injection molding standard small blocks. These blocks are injection molded at 25 ° C or 280t. 各 The ingredients used in the examples are as follows: A weight average A rubber with a particle size of 0.4 micron, which contains a styrene / acrylic copolymer grafted on the core-shell structure matrix. The core contains styrene and the shell is a cross-linked polyacrylic acid. The relative amounts of styrene and acrylonitrile in the dendritic phase (8 / such as ratio) The f difference between Examples 1, 2 and 3 (representing the present invention) and Comparative Examples C-1 and c_2 is the same. The number of S / AN is average And weight average molecular weight are each kg / mole and 108 kg / mole. The core-shell junctions used in the examples The amount of styrene as the core in the core is 5% of the core-shell structure weight. Ί -------- Q (please read the precautions on the back before filling this page). System -f, ί I n I an 1 I λα.-^ Βϋ I ϋ nn ϋ an nn 1 i = 口惠 ^ 一 、-Μ ° shape toward + Guanvalger X 297 mm) A7 V. Description of the invention ( 14) and butyl acrylate shell content is 95%. The first graft phase (P1) is made of styrene and acrylonitrile in different ratios in the presence of a core-shell structure rubber matrix (the amount of styrene is listed in the table ) Polymerized. For all examples and δ, the weight ratio of total monomers (acetophenone and acrylonitrile) to core-shell rubber is 0.325 / 1. The subsequent graft phase (P2) is based on the previously grafted matrix. In the presence of styrene and acrylonitrile polymerized at a weight ratio of S / AN = 70/30. For all examples' total monomers (styrene and acrylonitrile) relative to the graft core_shell rubber's The weight ratio is 0.325 / 1. The degree of grafting obtained by grafting rubber is 31.5%, based on the grafting rubber. Base polymer substrate: an S / The AN copolymer substrate has an AN content of 32% by weight of the copolymer, and the number average and weight average molecular weight of S / AN are 54 kg / mol and 118 kg / mol, respectively. Details of the polymerization steps: A clean, five-liter glass reactor was charged with deionized water and styrene-co-acrylonitrile (70% styrene seed latex, particle size = 85-100 nm, 1.5 parts solids). This reaction The device was equipped with a temperature control system, a nitrogen filling device, a reflux condenser and a stirrer. The initial filling was stirred at 220 rpm and heated to 85 t under a nitrogen purge :. At 85 ° C, first fill the potassium persulfate solution into the reactor (0.225 parts of solids) to start the batch reaction. Start to add styrene (3.482 parts) and diene at a rate that can be added within 15 minutes. Propyl maleate (0.018 The reverse of this paper applies the Chinese National Standard (CNS) A4 specification (210x 297 mm)) :! ο! (Please read the precautions on the back before filling this page) Order · --- ------- Line! Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ----------------------- '_ Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumption Cooperative printed A7 ^ -V. Invention Description (14-1) parts) and started to add a sodium hydrogen peroxide (0 · 100 parts) and potassium persulfate at a rate that could be added within 370 minutes. (0.360 parts) of water. At 30 minutes, a large amount of room temperature deionized water was filled to cool the batch to 65 ° C and maintained at this temperature throughout the rubber polymerization process. At 45 minutes, add the first surfactant solution-CalfaxDB45 "(1.25 parts solids) to the amount of water flow, and begin to add butyl acrylate ( 94.4 parts), a diallyl maleate (0.600 parts) and a second surfactant, Aerosol TR-702) (0.400 parts). At 225 minutes, raise the batch temperature to 80 ° C. This temperature was maintained throughout the graft polymerization process. At 240 minutes, a mixture of styrene (22.750 to 32.50 parts) and acrylonitrile (9.75 to 0.00 parts) was started to be weighed in. The total amount of styrene and acrylonitrile Keep constant (32 · 50 parts), and control the speed to complete the addition within 300 minutes. At 300 minutes, add styrene (22.75 parts) and acrylonitrile at the speed that can be completed within 360 minutes. (9.75 parts) mixture. This batch is completed and cooled at 390 minutes. In i! ---- Q) — — (Please read the notes on the back before filling this page) Order. --- I- --- Line! Note ": Calfax DB-45 is 46% water soluble by Pilot Chemical Co. -1 6-1-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) A7 Stamped by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ B7_ V. Description of the invention (14-3 liquid type; this substance It is a mixture consisting of the following components in the following approximate proportions: a. Dodecyl (branched) diphenyl oxide disulfonic acid disodium salt ... 86% b. Dodecyl (branched) di Phenyl oxide monosulfonic acid sodium salt --- 7% c. Di-dodecyl (branched) diphenyl oxide disulfonic acid sodium salt --5% d. Di-dodecyl ( Branched) Diphenyl oxide monosulfonic acid sodium salt ... 2% Note 2): Aerosol TR-70 is provided by Cytec Industries Inc. as 70% 2/1 ethanol / water solution; this substance is ditridecyl sulfur Substituted sodium succinate ° — (Please read the precautions on the back before filling this page) _ί Example 1 2 3 C-1 C-2 Styrene in the first graft phase 80 85 90 100 70 (% by weight ) MMP⑴, psi 667 653 638 638 682 Opacity (ii) Impact properties 97.7 97.4 97.5 97.3 97.9 Cantilever type, 1/8 ", Joules / meter at 23 ° C 333 501 381 301 284 at -30 ° C 45 43 47 30 36 Impact type cantilever type, 1/2 ", Joule / meter -16-2-This paper & degree applies to China National Standard (CNS) A4 (210 X 297 male) (%) Order ---------- Line 丨 15. Invention Description () 5) Printed by A7 B7 at 23 ° C 181 297 176 113 176 at -30 ° C 69 74 68 40 48 Multi-vehicle impact (111), Joule Er @ 23〇C 86 38 37 36 37 Et @ -30 ° C 10 17 13 8 8 Yellow index 29.7 29.1 28.8 28.6 31.0 Reflection turbidity 51.6 50.0 45.6 33.4 61.3 Gloss (20. ) 84.3 85.2 85.1 89.6 79.5 Gloss (60.) 96.1 96.3 96.7 97.6 93.3 ⑴ mmp = Minimum molding pressure, measured at 490 ° C (") The control ratio explained below (out) measured according to ASTM D3763; Ef refers to The minimum molding pressure at which the energy required for failure is a melting temperature of 255 C is the composition flowability index. The data indicates that the impact strength and opacity depend precisely on the composition's graft phase. The control ratio (CR) is An opacity measurement, which is measured on a molded sample of 3x4x0.1 pairs taken. This measurement is limited to a spectrophotometer (Applied Co) or System; using a light source D65 at an observation angle of 0 ° The reflection on the black background is then measured on the white background. The Y-second stimulus value can be calculated based on the three-device CIE (International Commission on Illumination) L *, f, and b * values. The control ratio (CR) is given by CR = 100 × γ (for black) / γ (for white) -17 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 0262 ^ ^ 0262 ^

Although it has been printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the present invention for the purpose of illustration, the description of the invention (] 6) has been explained for the sake of detail only, but it can be used for this purpose. This technique can be performed in the basin without the spirit and scope of this volume, except that it may be limited by the scope of patent application. This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 mm)

Claims (1)

六 Applicable Patent Scope Specialist Application No. 88106795 ROC ^ | ent Appln. No. 88106795 Amended Application of Chinese Text-Annex I Amended Glamxa m Cluixti ^ e — EnCtrT " (Submitted on January 2, 89) ( Submitted on January [|, 2000) (Please read the notes on the back before filling out this page) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a thermoplastic molding composition containing a grafted rubber and a copolymer substrate. The graft rubber includes a matrix, a first graft phase, and a subsequent graft phase that is then grafted onto the matrix, wherein the matrix includes a crosslinked elastomer selected from the group consisting of polyalkylacrylates, polyhydrodiene, and polydiene. Olefin and the first graft phase comprise a copolymer comprising 75 to 100% by weight of the vinyl aromatic monomer and 0 to 25% by weight selected from the group consisting of (fluorenyl) acrylonitrile A copolymer formed with a member of the alkyl (meth) acrylate family, wherein the subsequent graft phase comprises a copolymer comprising 60 to 75% by weight of the vinyl aromatic monomer of the subsequent graft phase and Account for that follow-up A copolymer formed from a member selected from the second group comprising (meth) acrylonitrile and an alkyl (meth) acrylate in an amount of 25 to 40% by weight of the branch phase, and wherein the first graft phase is relative to the The weight ratio of the subsequent graft phase is 1/4 to 4/1, the graft rubber exists in the form of particles with a weight average particle diameter of 0.1 to 1.0 micron, and wherein the substrate contains a vinyl aromatic monomer and an optional A self-contained polymerization product of a (fluorenyl) acrylonitrile and an alkyl (fluorenyl) acrylate monomer, the first graft phase and the subsequent graft phase are chemically different from each other; and wherein the graft The rubber is present in an amount of 15 to 50% by weight and the copolymer substrate is present in an amount of 50 to 85%, and the percentage of both is relative to the total amount of the composition. 2. The thermoplastic molding composition according to item 1 of the scope of the patent application, wherein the matrix contains a core of a polymer product containing a vinyl aromatic monomer, and the Chinese national standard (CNS) A4 specification (210) applies to this paper size (210 X 297 mm) 6 Application for Patent Scope Specialist Application No. 88106795 ROC ^ | ent Appln. No. 88106795 Amendment of the Application Form Chinese Text-Annex I Amended Glamxa m Cluixti ^ e — EnCtrT " (January 89 (Submitted on January [|, 2000) (Please read the notes on the back before filling out this page) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a thermoplastic molding containing grafted rubber and copolymer substrate A composition wherein the graft rubber includes a matrix, a first graft phase, and a subsequent graft phase that is then grafted onto the matrix, wherein the matrix includes a crosslinked elastomer selected from the group consisting of polyalkylacrylates, polyhydrogenates Diene and polydiene, and the first grafted phase comprises a copolymer which is a vinyl aromatic monomer which comprises 75 to 100% by weight of the copolymer and 0 to 25% by weight A copolymer comprising a member of the (fluorenyl) acrylonitrile and alkyl (meth) acrylate family, wherein the subsequent graft phase comprises a copolymer that accounts for 60 to 75% of the weight of the subsequent graft phase A copolymer formed by a vinyl aromatic monomer and a member selected from the second group comprising (meth) acrylonitrile and an alkyl (meth) acrylate, comprising 25 to 40% by weight of the subsequent graft phase, And wherein the weight ratio of the first graft phase to the subsequent graft phase is 1/4 to 4/1, the graft rubber exists in the form of particles having a weight average particle diameter of 0.1 to 1.0 microns, and wherein the The substrate contains a vinyl aromatic monomer and a polymerization product selected from the group consisting of (fluorenyl) acrylonitrile and alkyl (fluorenyl) acrylate monomers. The first graft phase and the subsequent graft phase are chemically Are different from each other; and wherein the graft rubber is present in an amount of 15 to 50% by weight and the copolymer substrate is present in an amount of 50 to 85%, and the percentage of the two is relative to the total of the composition the amount. 2. The thermoplastic molding composition according to item 1 of the scope of the patent application, wherein the matrix contains a core of a polymer product containing a vinyl aromatic monomer, and the Chinese national standard (CNS) A4 specification (210) applies to this paper size (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 6. Scope of patent application and a layer containing a crosslinked rubber shell selected from polyhexyl acrylic acid, polyhydrodiene and polydiene . 3. The thermoplastic molding composition according to item 1 of the patent application scope, which comprises (a) 15 to 50% of a graft rubber (GR) and (b) 85 to 50% of a copolymer matrix (MX), both The presence of 'the percentage is relative to the total of (GR) and (Μχ), where the grafted rubber (GR) includes a matrix, a first graft phase (ρι), and a subsequent graft phase (P2)' where the first The graft phase and subsequent grafting are like sequentially grafted onto the substrate, and then the graft phase is grafted onto the substrate in a conventional manner and its (S) / (P1 + P2) weight ratio is 60/40 to 90 / Within the range of 10, and wherein the first graft phase (P1) comprises a monomer selected from the group consisting of styrene, α-fluorenyl styrene, cyclohydrostyrene and cycloalkylated styrene (3GP), and A copolymer comprising (fluorenyl) acrylonitrile and a monomer of methyl methacrylate (4GP), the (3GP) comonomer is present in an amount of 75 to 100% by weight of the (P1). % And the (4GP) comonomer is present in an amount of 0 to 25% by weight of the (P1), and the (P2) contains a group selected from the group consisting of styrene, α-methylstyrene, and cyclohydrogen. A copolymer of styrene and cyclo-fired styrene-vinyl (5GP) monomers and monomers selected from monomers including (meth) acrylonitrile and methacrylate (6GP), which (5GP) The comonomer is present in an amount of 60 to 75% by weight of the subsequent graft phase (P2) and the (6GP) comonomer is present in an amount of 25 to 40% by weight of (P2). And where (P1 / P2) weight ratio is 1/4 to 4/1, the first graft phase (pi) and the subsequent graft phase -20- (CNS M4 specification (21〇χγ9ϋ) ---- ( Please read the notes on the back before filling out this page) 9 :: m ^ — I m ^ 1 ^ 1. M * i ^^^ 1 I--n I--^ Toj.-1 ^ 1 Color "A8 B8 C8 D8 VI. The scope of patent application (P2) is chemically different from each other. The graft rubber exists in the form of particles with a weight average particle diameter of 0.1 to 10 microns. The copolymer substrate contains a material selected from the group consisting of phenylethyl晞, α_methylstyrene, cyclic hydrogenated benzene (please read the notes on the back before filling out this page) Co-monomers of ethylene and cycloalkylated styrene (MX1) family and selected from the group consisting of (fluorenyl) Acrylonitrile and methyl methacrylate () ^ 2) comonomers, where the weight ratio of (MX1) / (MX2) ranges from 80/2/65 to 65/35. 4_ According to the patent application The thermoplastic molding composition of the range item 3, wherein the (S) / (P1 + P2) weight ratio is in the range of 70 to 80 to 30 to 20. 5. The thermoplastic molding composition of the range 3 item according to the patent application Where (P1 / P 2) The weight ratio is 33/67 to 67/33. 6. The thermoplastic molding composition according to item 3 of the patent application range, wherein the (P1 / P2) weight ratio is 1/2 to 2/1. 7 According to Shen The thermoplastic molding composition according to the third item of the patent, wherein the weight average particle size is 0.25 to 0.65 microns. 8 _ The composition according to the first claim of the patent, wherein the matrix (s) contains the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Print a core (C) and the shell (SH) that surrounds the core, with a (C) / (SH) weight ratio of 1/99 to 25/75 and the (C) is selected from the group consisting of styrene , Α-fluorenylstyrene, cyclohydrostyrene, and cycloalkylated styrene members are polymerized and its shell (SH) contains a member selected from the group consisting of polyalkyl acrylates, polyhydrogenated dienes, and polydienes. Crosslinked oak. 9. The composition according to item 8 of the scope of patent application, wherein the core (c) is crosslinked. -21-(CNS) A4 «, ^-(210X297 ^^)-~~